Kinetics Best

13
13.1
13.2
13.3
13.4
Rates of Chemical
Reactions
Rates of Chemical Reactions
Expressions of Reaction Rates in Terms of
Rates of Changes in Concentrations of
Reactants or Products
Methods of Measuring Reaction Rates
Factors Affecting Reaction Rates
Chemical Kinetics
A study of
(1)
reaction rates
(2)
the factors affecting reaction rates
(3)
reaction mechanisms
(the detailed steps involved in

reactions)
Explosive reactions
2H2(g) + O2(g) 2H2O(l)
Vigorous reactions
2K(s) + 2H2O(l) 2KOH(aq) + H2(g)
Potassium reacts with

water vigorously
4
Very rapid reactions

Formation of insoluble salts
+
Ag (aq) + Cl (aq) AgCl(s)

Formation of insoluble bases
Fe3+(aq) + 3OH(aq) Fe(OH)3(s)

Acid-alkali neutralization reactions
H (aq) + OH (aq) H2O(l)

+
Q.1
+
Ag (aq) + Cl (aq) AgCl(s)

Fe3+(aq) + 3OH(aq) Fe(OH)3(s)
H (aq) + OH (aq) H2O(l)

+
All involve oppositely charged ions
Rapid or moderate reactions

Displacement reactions of metals : Zn(s) + 2Ag+(aq) Zn2+(aq) + 2Ag(s)
Rapid or moderate reactions

Displacement reactions of metals : Zn(s) + 2Ag+(aq) Zn2+(aq) + 2Ag(s)
Displacement reactions of halogens : Cl2(aq) + 2Br(aq) 2Cl(aq) + Br2(aq)
10
Slow reactions
Fermentation of glucose
C6H12O6(aq) 2C2H5OH(aq) + 2CO2(g)
11
Slow reactions
2MnO4(aq) + 5C2O42(aq) + 16H+(aq)
12
2Mn2+(aq) + 10CO2(g) + 8H2O(l)
Very slow reactions

Rusting of iron
4Fe(s) + 3O2(g) + 2nH2O(l) 2Fe2O3 nH2O(s)
13
Extremely slow reactions

CaCO3(s) + 2H+(aq) Ca2+(aq) + CO2(g) + H2O(l)
Before corrosion
14
After corrosion
Two Ways to Express Reaction Rates

1. Average rate
2. Instantaneous rate
(rate at a given instant)
15
Average rate of reaction

Total change in amount of a product or a reactant
Total time taken for the change to occur
Amount is usually expressed in

Concentration
Mass
Volume
Pressure
16
mol dm3
g
cm3 or dm3
atm
Q.2 0.36 g of magnesium reacted with 50.0 cm3

of 1.0 M hydrochloric acid to give 360 cm3 of
hydrogen under room conditions.
The reaction was completely in 90 seconds.
Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)
0.36 g
3
1
(a) Average rate
4.0 10 g s
90 s
17
Q.2 0.36 g of magnesium reacted with 50.0 cm3

of 1.0 M hydrochloric acid to give 360 cm3 of
hydrogen under room conditions.
The reaction was completely in 90 seconds.
360 cm
(b) Average rate
4.0 cm3 s 1
90 s
3
18
2.
(c)

0.36 g
No. of moles of Mg
0.015 mol
1
24.3 g mol
No. of moles of HCl 1.0 mol dm 3 0.0500 dm3 0.0500 mol
Mg is the limiting reactant

No. of moles of HCl reacted 2 0.015 mol 0.030 mol
Decrease in concentration of HCl(aq) in 90 s
0.030 mol
3
0.60
mol
dm
0.0500 dm3
0.60 mol dm-3

Average rate
6.7 10-3 mol dm-3 s 1
90 s
19
2.
(d)
Rate of reaction
Rate of reaction
= 2
w.r.t. HCl(aq)
w.r.t. MgCl2(aq)
Increase in concentration of MgCl2(aq) in 90 s
1
0.60 mol dm 3 0.30 mol dm-3
2
0.30 mol dm-3

Average rate
3.3 10-3 mol dm-3 s 1
90 s
20
The rate at a particular instant of the
reaction is called the instantaneous rate.
For the chemical reaction
aA + bB cC + dD
Instantaneous rate
d[A] 1
d[B] 1
d[C] 1
d[D] 1
( )
( )
( )
( )
dt
a
dt b
dt c
dt d
[X] = molarity of X
21
The rate at a particular instant of the
reaction is called the instantaneous rate.
For the chemical reaction
aA + bB cC + dD
Instantaneous rate
d[A] 1
d[B] 1
d[C] 1
d[D] 1
( )
( )
( )
( )
dt
a
dt b
dt c
dt d
Units : mol dm3 s1, mol dm3 min1, mol dm3 h1etc.
22
Graphical Representation of Reaction

Rates Rate curves
A rate curve is a graph plotting the amount of
a reactant or product against time.
23
Consider the reaction

A
(reactant)
24
+ C
(product)
At any time t, the instantaneous rate of the

reaction equals the slope of the tangent to the
curve at that point.
The greater the slope, the higher the rate of the
reaction.
25
-ve slope of curve of reactant A

[A] with time
26
+ve slope of curve of product B

[B] with time
27
The rate at t0 is usually the fastest and is called

the initial rate.
The curve is the steepest with the greatest
slope at time t0.
28
The rate of the reaction gradually as the

reaction proceeds.
Flat curve
reaction completed
29
Concentration of product Z
(mol dm3)
Q.3
30
X + Y 2Z
C
B
A
Time of reaction (min)
(mol dm3)
1 5.4 mol dm 3
Average rate
0.39 mol dm 3 min 1
2
7 min
31
X + Y 2Z
C
B
A
(mol dm3)
X + Y 2Z
32
C
B
Instantaneous rate at A
1 (6.0 - 0.0) mol dm 3

2
(1.6 - 0.0) min
1.9 mol dm 3 min 1
1.6
(mol dm3)
X + Y 2Z
33
5.1
B
2.7
Instantaneous rate at B
1 (5.1 - 2.7) mol dm3

2
(3.0 - 1.0) min
0.6 mol dm 3 min 1
A
(mol dm3)
X + Y 2Z
34
C
B
Instantaneous rate at C 0
A
Methods of Measuring Reaction Rates

A. Physical measurements
1. Continuous measurements
2 Initial rate measurements
(Clock reactions)
B. Chemical measurements (Titration)
35
1. Continuous measurements
Experiment is done in ONE take.
The reaction rates are determined by
measuring continuously a convenient property
which is directly proportional to the
concentration of any one reactant or product
of the reaction mixture.
36
Properties to be measured :
Gas volume / Gas pressure / Mass /
Color intensity / Electrical
conductivity
1.1 Measurement of large volume changes

Examples:
(1) CaCO3(s) + 2HCl(aq)
CaCl2(aq) +
H2O(l) + CO2(g)
(2) Zn(s) + H2SO4(aq)
ZnSO4(aq) + H2(g)
37
(3) 2H2O2(aq)
2H2O(l) + O2(g)
1.1 Measurement of large volume changes
Temperature is
kept constant
38
A typical laboratory set-up for measuring the

volume of gas formed in a reaction
Volume of gas formed (cm3)
Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)
39
dV
slope
rate
dt
Q.4
(2) Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)
H2(g) is sparingly soluble in water while

CO2 is quite soluble in water.
Volume
of CO2
Rate
Rate
40
Sigmoid curve
1.2 Measurement of small volume changes

- Dilatometry
Capillary tube
Liquid phase reaction

mixture
CH3COOH(l) + CH3CH2OH(l) CH3COOCH2CH3(l) + H2O(l)
41
1.3 Measurement of mass changes

CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)
42
The cotton wool plug is to allow the escape of CO2(g) but

to prevent loss of acid spray due to spurting.
stopwatch
cotton wool plug
limestone pieces
of known mass
measured volume of
standard
hydrochloric acid
electronic
balance
43
Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)
CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)

Which reaction is more suitable to be followed
by mass measurement ?
Hydrogen is a very light gas.
The change in mass of the reaction mixture
may be very small.
The electronic balance used in the school
laboratory may not be sensitive enough to
detect the small change.
44
Loss of mass (m)
mfinal = total mass loss
dm
slope
rate
dt
time
m final - m t
45
mfinal = mfinal m0
( m0 = 0)
d[H ]
slope
= rate 2
dt
time
1.4 Colorimetry
colour intensity [coloured species]
d(colour intensity)
rate
dt
46
H2O2(aq) + 2H+(aq) + 2I(aq) I2(aq) + 2H2O(l)
colour intensity as reaction proceeds

CH3COCH3(aq) + I2(aq)
CH3COCH2I(aq) + H+(aq) + I(aq)
Br2(aq) + HCOOH(aq)
2H+(aq) + 2Br(aq) + CO2(g)
2MnO4(aq) + 16H+(aq) + 5C2O42(aq)
2Mn2+(aq) + 10CO2(g) + 8H2O(l)
colour intensity as reaction proceeds

47
48
cuvettes
A colorimeter
49
Yellow
light
Yellow
filter
Blue solution
Complementary colours
50
Red Cyan
Pairs of opposite colours are complementary

colours
51
Red Cyan
Green Magenta

colours
52
Red Cyan
Green Magenta
Blue Yellow
CMYK
colours
53
When mixed in the proper proportion,

complementary colours produce a neutral color
(grey, white, or black).
54
I0
I0 = intensity before absorption

I = intensity after absorption
55
I0
I
100%
% transmittance
I0
56
I0
Absorbance log10
If I = I0 ,
If I = 0 ,
%T = 100%
%T = 0%
A = log101 = 0
A log10
zero absorption
complete absorption
A = bC
Beers law
57
Deviation at higher
concentrations
A calibration curve is first

constructed for AC conversion
C
58
Q.5
[I2]
d[I2 ]
slope
rate
dt
time
A
dA
slope
rate
dt
59
time
1.5 Measurement of electrical

conductivity
Na+OH(aq) + CH3COOH(aq) CH3COONa+(aq) + H2O(l)
conducting mobility : OH > CH3COO
conductivity as the rx proceeds
60
1.5 Measurement of electrical

conductivity
2MnO4(aq) + 16H+(aq) + 5C2O42(aq)
2Mn2+(aq) + 10CO2(g) + 8H2O(l)
total number of ions
electrical conductivity as the rx proceeds
61
1.6 Measurement of pressure changes
d(PT )
rate
dt
PT = total pressure of the reaction
mixture
62
Q.6
(i)
(ii)
2NO(g) + 2H2(g) N2(g) + 2H2O(g)

3H2(g) + N2(g) 2NH3(g)
At fixed V and T, PT n
In both reactions,
n as the reactions proceed
PT as the reactions proceed
63
suction
flask
dilute hydrochloric acid
magnesium ribbon
pressure sensor
to data-logger
interface and computer

64
A(g) + B(g) products
65
A chemical clock is a complex mixture of

reacting chemical compounds in which the
concentration of one or more components
exhibits periodic changes.
In cases where one of the reagents has a
visible color, crossing a concentration
threshold can lead to an abrupt color change in
a reproducible time lapse.
66
2. Initial Rate Measurements-Clock Reactions

1. A set of experiments is done in which all
reaction conditions but one are kept constant.
S2O32(aq) + 2H+(aq) SO2(aq) + H2O(l) + S(s)
67
Experiment
[S2O32(aq)] / M
[H+(aq)] / M
0.10
0.08
0.04
0.02
2. Initial Rate Measurements-Clock Reactions

yellow
precipitate
2. The time taken for the reaction to arrive at a
particular point at the early stage of the
reaction is measured.
68
The beaker containing the reaction mixture is

placed over a cross marked on a white tile.
69
As more sulphur forms, the reaction mixture

becomes more cloudy.
70
The cross becomes more and more difficult to

see and finally disappears.
71
Average rate in the early stage

=
yellow
precipitate
Amount of S required to blot out the mark

Time taken to blot out the mark
Since the amount of S required to blot out

the mark is a constant,
1
Average
rate
time taken to blot out the mark
72
1
Average
rate
time taken to blot out the mark
The average rate of reaction is inversely

proportional to the time taken to blot out the
mark.
The faster is the reaction, the shorter is the
time taken for the mark to disappear.
73
dS
dt
S
slope average rate
t
slope initial rate
amount of S
If S and t are small(early stage)
dS S
dt t
time
74
dS S
dt t
Since S is a constant
dS S 1
dt t t
75
Initial rate k[S2O32(aq)]x[H+(aq)]y
Since HCl is in large excess,

[H+(aq)]y constant at the early stage
Initial rate k[S2O32(aq)]x[H+(aq)]y k[S2O32(aq)]x
S 1
Initial rate
t t
1
2
''
k [S2O3 (aq)]x
t
76
0.10
Time taken
(t)
to mask the
mark / s
10
0.08
13
0.04
25
0.02
50
Expt.
77
[S2O3 (aq)] [H (aq)]

(M)
(M)
2
1
t
/ s1
Q.7
1
t
1 ''
2
x
k [S2O3 (aq)]
t
Linear x = 1
[S2O32(aq)]
78
Other Examples of Clock Reactions : 5I(aq) + IO3(aq) + 6H+(aq) 3I2(aq) + 3H2O(l)

Small and fixed amounts of S2O32(aq) and starch are
added to the reaction mixtures in all runs.
I2(aq) + 2S2O32(aq) 2I(aq) + S4O62(aq)
(fixed) (fixed)
I2(aq)
starch deep blue complex
(excess) (fixed)
Time taken for the reaction mixture to turn deep blue
is measured.
79
Other Examples of Clock Reactions : 5I(aq) + IO3(aq) + 6H+(aq) 3I2(aq) + 3H2O(l)

I2(aq) + 2S2O32(aq) 2I(aq) + S4O62(aq)
(fixed) (fixed)
I2(aq)
(excess)
starch deep blue complex

(fixed)
By changing the concentration of any one of the

reactants, deep blue colour will appear in different
time lapses a chemical clock !
Halloween clock
80
Other Examples of Clock Reactions : 5Br(aq) + BrO3(aq) + 6H+(aq) 3Br2(aq) +

OH
3H2OH
O(l)
Br
(fixed)
Br2
(excess)
81
Br
3Br2
(fixed)
Br
methyl red colourless

(fixed)
Advantages of physical measurements

1. Suitable for fast reactions.
2. Small sample size
3. More accurate than chemical method
(titration)
4. No interruption continuous measurements
5. Can be automated.
82
Disadvantages of physical measurements

1. More sophisticated
2. More expensive
3. More specific only suit a limited number of
reactions.
83
B. Chemical Measurements (Titration Methods)

1. Start a reaction with all reaction conditions
but one fixed.
2. Withdraw and quench fixed amounts of the
reaction mixture at different times.
84
Quenching methods:
Temperature
Cooling the reaction mixture rapidly in ice.

Diluting the reaction mixture with a
sufficient amount of cold water or an
appropriate solvent. Concentration
Removing one of the reactants or the
catalyst (if any) by adding another
reagent.
85
B. Chemical Measurements (Titration Methods)

1. Start a reaction with all reaction conditions
but one fixed.
2. Withdraw and quench fixed amounts of the
reaction mixture at different times.
3. Titrate the quenched samples to determine
the concentration of one of the reactants or
products.
86
CH3COCH3 + I2
H+ as catalyst
CH3COCH2I + HI
Q.8
The reaction is quenched by adding to it NaHCO 3(aq)
that removes the catalyst.
HCO3(aq) + H+(aq) H2O(l) + CO2(g)
87
CH3COCH3 + I2
H+ as catalyst
CH3COCH2I + HI
Q.9
Titrated with standard solution of Na2S2O3(aq) using
starch as indicator (added when the end point is near)
2S2O32(aq) + I2(aq) S4O62(aq) + 2I(aq)

Colour change at the end point : deep blue to colourless
88
CH3COCH3 + I2
H+ as catalyst
CH3COCH2I + HI
Q.10
The excess S2O32(aq) would react with H+ to give a
cloudy mixture with a pungent smell.
S2O32(aq) + 2H+(aq) S(s) + SO2(g) + H2O(l)
89
Advantages of titrimetric method

1. Only simple apparatus are required.
2. Can be applied to a great variety of slow
reactions.
90
Disadvantages of physical measurements

1. Not suitable for fast reactions.
It takes time to withdraw samples and
perform titration.
2. Reactions are disturbed NOT continuous
3. Time consuming NOT automated
91
Factors
Affecting
Reaction Rates
92
Collision Theory
No reaction
Sufficient K.E.
Incorrect orientation
93
Collision Theory
No reaction
Correct orientation
Insufficient K.E.
94
Collision Theory
Sufficient K.E.
Correct orientation
Effective collision
95
Collision Theory
Activation energy
Bond breaking and bond forming occur at the

same time
Ea < B.E.(s) of the bond(s) to be broken
96
Collision Theory
Activation energy
Higher Ea
more K.E. required for effective collision
slower reaction
97
Collision Theory
Activation energy
Lower Ea
less K.E. required for effective collision
faster reaction
98
Collision Theory
Activation energy
Rate of reaction depends on Ea which in turn

depends on the nature of reactants.
E.g. K is more reactive than Mg
99
Factors Affecting Reaction Rates

concentration
concentration
100
particle size
size
particle
pressure
pressure
catalyst
catalyst
temperature
temperature
light
light
Effect of concentration
101
e.g. Reaction between Mg and HCl
(a) 2.0
2.0 M
M HCl
HCl
(a)
(b) 1.0
1.0 M
M HCl
HCl
(b)
(c) 0.5
0.5 M
M HCl
HCl
(c)
Reaction rate:
rate:
Reaction
(a) >> (b)
(b) >> (c)
(c)
(a)
102
Time for
for reaction
reaction to
to
Time
complete: tt11 << tt22 << tt33
complete:
Higher [HCl(aq)]
[HCl(aq)]
Higher
Faster
Faster reaction
reaction
103
[X]
Reactant particles are more crowded
Collision frequency
Number of effective collisions
Reaction rate
104
For the reaction
aA + bB cC + dD
Rate k[A]x[B]y
where x and y are the orders of reaction
with respect to A and B
k is the rate constant
units mol dm3 s1/(mol dm3)x+y
105
For the reaction
aA + bB cC + dD
Rate k[A]x[B]y
x and y can be integers or fractional
x y is the overall order of reaction.
x, y can ONLY be determined experimentally.
106
Effect of pressure
Only applicable to reactions involving gaseous
reactants.
107
Pressure
Reactant particles are more crowded
Collision frequency
No. of effective collisions
Rate of reaction
108
Effect of temperature
Applicable to ALL reactions
109
T
K.E. of particles
Collision frequency (minor effect) and
No. of particles with K.E. > Ea (major effect)
No. of effective collisions
Rate of reaction
110
Rate
Rate of reaction
exponentially with temperature
Rate e
Ea
RT
In general, a 10oC in T
doubles the rate.
T / C
111
Effect of particle size

For a fixed volume of solid,
Smaller particle size greater surface area
112
CaCO3(aq) + 2H+(excess) CaCl2(aq) + H2O(l) + CO2(g)
Rate involving
involving
Rate
powdered solid
solid
powdered
reactant is
is higher
higher
reactant
Reason: higher
higher
Reason:
chance of
of contact
contact
chance
between reactant
reactant
between
particles
particles
113
Q.11
0.5 g powder
0.5 g granule
114
Effect of Catalyst
A catalyst is a substance that alters the rate
of a chemical reaction by providing an
alternative reaction pathway with a different
activation energy.
A positive catalyst speeds up a reaction by
providing an alternative reaction pathway
with a lower Ea.
115
A negative catalyst slows down a reaction

by providing an alternative reaction pathway
with a higher Ea.
Effect of Catalyst
Catalysts remain chemically unchanged at the
end of reactions.
116
H2O2(aq)
MnO2 as catalyst
2H 2O(l) + O2(g)
Physical measurement
117
2H 2O(l) + O2(g)
Volume of gas formed (cm3)
H2O2(aq)
MnO2 as catalyst
118
Titrimetric method (Q.12)

H2O2(aq)
MnO2 as catalyst
2H 2O(l) + O2(g)
Pipette samples at different times

Remove MnO2(s) by filtration
Titrate with MnO4(aq)/H+(aq)
5H2O2(aq) + 2MnO4(aq) + 6H+(aq)
2Mn2+(aq) + 8H2O(l) + 5O2(g)
119
Q.13
[H2O2
]
Without MnO2
With MnO2
time
120
Effect of light
Light with specific frequency (E h) can
provide sufficient energy to break a particular
chemical bond in a reactant leading to a
photochemical reaction.
Br Br
Br + Br
C6H14 + Br C6H13 + HBr

C6H13Br
121
Autocatalysis
Catalysis in which the product acts as the
catalyst of the reaction
2MnO4(aq) + 16H+(aq) + 5C2O42(aq)
2Mn2+(aq) + 10CO2(g) + 8H2O(l)
CH3COCH3(aq) + I2(aq)
CH3COCH2I(aq) + H+(aq) + I(aq)
122
Q.14
[MnO4]
Rate
Sigmoid curve
Rate
123
time
The END
124
13.1 Rates of Chemical Reactions (SB p.5)
Back
In a chemical reaction, a total of 0.18 g of
carbon dioxide gas is given out in 1 minute
at room temperature. What is its average
rate in mol s1 for that time interval?
Number of moles of CO2 =
0.18 g
(12.0 16.0 2) g mol - 1
= 0.0041 mol
0.0041 mol
Average rate =
60 s
125
= 6.83 105 mol s1
Answer
In the uncatalyzed decomposition of

hydrogen peroxide solution into water
and oxygen at room conditions, the
volume of oxygen given out in 20 hours is
5 cm3. What is its average rate in mol s1
for that time interval?
2H2O2(l) 2H2O(l) + O2(g)
(Molar volume of gas at room temperature
and pressure= 24.0 dm3 mol1)
Answer
126
Back
Number of moles of O2
5 cm 3
=
24 000 cm 3 mol 1
= 2.08 104 mol
2.08 10 -4 mol
Average rate =
(20 60 60) s
= 2.89 109 mol s1
127
The change in
concentration of
reactant X in a
chemical reaction is
illustrated in the graph
on the right.
128
With the use of the graph, calculate

(a) the initial rate of the reaction;
(b) the average rate for the time
interval from
the 1st to the 2nd
minute;
(c) the instantaneous rate at the 3rd
minute.
1
(Give your answers in mol dm3 min
.)
Answer
129
(a) Initial rate

=
Slope of the tangent

to the curve at t0
(0.100 0.160) mol dm 3
=
(1.2 0) min
= -0.05 mol dm-3 min-1
130
(b) Average rate

(0.080 0.110) mol dm 3
=
(2 1) min
= -0.03 mol dm-3 min-1
131
Back
(c) Instantaneous rate at the

3rd minute
=
Slope of the tangent to

the curve at the 3rd
minute
3
(0.046
0.077)
mol
dm
=
(3.5 2) min
= -0.021 mol dm-3 min-1
132
(a) In the hydrolysis of an ester at a constant

temperature of 398 K, the concentration of
the ester decreases from
1 mol dm3 to 0.75 mol dm3 in 4 minutes.
What is its average rate in mol dm3 s1 for
that time interval?
Answer
(a) Average rate at 398 K
= (1 0.75) mol dm-3 (4 60) s
= 0.001 04 mol dm-3 s-1
133
(b) The graph on the right shows the

change in concentration
of
a reactant in a chemical reaction.
134
With the use of the graph above, calculate

(i)
the initial rate of the reaction;
(ii) the average rate for the time interval from

the 20th to the 30th second;
(iii) the instantaneous rate at the 10th second.
Answer
135
Back
(i)
Initial rate = (0.02 - 0.01) mol dm

(0 10) s
-3
= -1 10-3 mol dm-3 s-1

-3
(
0.009
0.006)
mol
dm
(ii) Average rate =
(20 30) s
= -3 10-4 mol dm-3 s-1

-3
(
0.018
0.013)
mol
dm
(iii) Instantaneous rate =
(0 10) s
= -5 10-4 mol dm-3 s-1

136
13.2 Expressions of Reactions Rates in Terms of Rates of Changes in

Concentrations of Reactants or Products (SB p.10)
Back
Haemoglobin (Hb) binds with carbon
monoxide according to the following
equation:
4Hb + 3CO
Hb4(CO)3
Express the rate of the reaction in terms of

the rate of change in concentration of any
Answer
ofthethe
reactants
oras:the product.
Theone
rate of
reaction
is expressed
d [Hb 4 (CO)3 ]
1 d [Hb]
1 d [CO]
Rate

dt
4
dt
3
dt
137
13.2 Expressions of Reactions Rates in Terms of Rates of Changes in

Concentrations of Reactants or Products (SB p.10)
Back
Express the rate of the following reaction in
terms of the rate of change in concentration of
any one of the reactants or the product.
2H2(g) + O2(g)
2H2O(l)
d [O 2 (g)]
1 d [H2 O(l)]
1 d [H2 ( g)]
Rate =
2
dt
2 dt
dt
138
Answer
13.3 Methods of Measuring Reaction Rates (SB p.11)
Alkaline hydrolysis of ethyl ethanoate (an

ester) using sodium hydroxide solution is
represented by the following equation:
CH3CO2CH2CH3(l) + NaOH(aq)
CH3CO2Na(aq) + CH3CH2OH(aq)
The rate of the reaction can be followed by

titrating small volumes of the reaction
mixture with standard dilute hydrochloric
acid at successive five-minute intervals.
139
(a) Suggest a method to quench the

reaction mixture so that the
concentration of sodium hydroxide
solution can be determined accurately.
Explain briefly why this method can
be
Answer
used.
(a) The reaction mixture can be quenched by pipetting a
sample of the reaction mixture into a conical flask
containing ice water. The cooling and dilution of the
reaction mixture decrease the reaction rate sufficiently for
chemical analysis.
140
(b) Explain why the change in concentration

of sodium hydroxide solution but not
that of ethyl ethanoate is measured in
order to determine the rate of the above
reaction.
Answer
(b) Sodium hydroxide is a strong alkali that reacts with strong
mineral acids almost instantaneously. Therefore, the
titration of sodium hydroxide solution and dilute
hydrochloric acid provides accurate experimental results.
141
Answer
(c) Explain which option, A or B, is a
reasonable set of experimental results
for the above titration.
Option A
Time after mixing
Volume of HCl
(min)
added at the end
point (cm3)
5
10
10
10
10
Option B
Time after mixing
Volume of HCl
(min)
added at the end
point (cm3)
142
(c) Sodium hydroxide is a reactant of the hydrolysis. As the

reaction proceeds, the concentration of sodium hydroxide
in the reaction mixture decreases with time, and hence
the amount of dilute hydrochloric acid used in the titration.
Thus, option A is a reasonable set of experimental results.
143
(d) Name a suitable indicator for the

titration.
(d) Methyl orange / Phenophthalein
Back
144
Answer
A student recorded the following

experimental results for the reaction of zinc
and dilute hydrochloric acid.
Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)
Time
0.0 1. 2. 3. 4. 5.0 6. 7. 8. 9.
(min)
0 0
0
0
0 0 0
0
Volume
of H2(g)
produce
d (cm3)
145
15 26 33 38
40
41 42 42 42
(a) Plot a graph of volume of hydrogen gas

produced against time.
(a)
146
Answer
(b) Describe the change in the rate of the

reaction using your graph in (a).
Answer
(b) As shown in the graph in (a), the volume of hydrogen

gas given out at the beginning of the reaction (e.g. in
the time interval between the 1st and the 2nd minute) is
greater than that near the end of the reaction (e.g. in
the time interval between the 6th and the 7th minute).
Therefore, the rate of the reaction decreases with time.
147
(c) Explain how you can measure the initial

rate of the reaction graphically.
Answer
(c) The initial rate can be found by determining the slope of

the tangent to the curve at time zero.
148
Back
(d) Determine graphically the rate of the
reaction at the 5th minute. State the unit.
Answer
(d) From the graph in (a),

rate of reaction
= slope of the tangent to the curve at the 5 minute
3
(46
34)
cm
=
(8 2) min
= 2 cm3 min-1
149
Back
Suggest an experimental method for
determining the rate of each of the following
reactions:
(a) S2O82(aq) + 2I(aq)
2SO42(aq) + I2( aq)
(b) CH3COOCH3(aq) + I2(aq)
CH3COOCH2I(aq) +
HI(aq)
(c) 2MnO4(aq) + 5C2O42(aq) + 16H+(aq)
(a) Colorimetric measurement / titration

(b) Colorimetric
measurement
2Mn2+(aq) + 10CO2(g)
mesurement / titration
+ (c)
H+Colorimetric
(aq)
150
Answer
+ 8H2O(l)
13.4 Factors Affecting Reaction Rates (SB p.17)
Explain why sawdust burns explosively in pure

oxygen but slowly in air.
A higher concentration of oxygen increases
the rate of combustion.
Back
151
Answer
(a) List THREE factors that affect the rate of a

chemical reaction.
Answer
(a) Concentration of reactants / pressure /

temperature / surface area / catalyst /
light (any 3)
152
(b) The figure below shows the laboratory setup for measuring the change in mass of the
reaction mixture with time in the course of
the reaction:
CaCO3(s) + 2HCl(aq)
CO2(g)
153
CaCl2(aq) + H2O(l) +
A certain mass of calcium carbonate was added

to 50 cm3 of 2.0 M hydrochloric acid at 20C.
Carbon dioxide was allowed to escape and the
mass of the reaction mixture was measured at
regular time intervals. The results were
expressed as the loss of mass with respect to
time. The experiment was carried out with one
change of condition at a time:
(i) using 1.0 M hydrochloric acid in place of 2.0
M
hydrochloric acid.
(ii) carrying out the reaction at 30C.
(iii) using powdered calcium carbonate of the
same mass.
154

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13

the factors affecting reaction rates

(the detailed steps involved in

Potassium reacts with

Very rapid reactions

Ag (aq) + Cl (aq) AgCl(s)

Very rapid reactions

Very rapid reactions

H (aq) + OH (aq) H2O(l)

Ag (aq) + Cl (aq) AgCl(s)

H (aq) + OH (aq) H2O(l)

All involve oppositely charged ions

Rapid or moderate reactions

Rapid or moderate reactions

2Mn2+(aq) + 10CO2(g) + 8H2O(l)

Very slow reactions

Extremely slow reactions

Two Ways to Express Reaction Rates

Average rate of reaction

Total time taken for the change to occur

Amount is usually expressed in

Q.2 0.36 g of magnesium reacted with 50.0 cm3

Q.2 0.36 g of magnesium reacted with 50.0 cm3

Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)

Mg is the limiting reactant

Decrease in concentration of HCl(aq) in 90 s

0.60 mol dm-3

Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)

0.30 mol dm-3

Graphical Representation of Reaction

Consider the reaction

At any time t, the instantaneous rate of the

-ve slope of curve of reactant A

+ve slope of curve of product B

The rate at t0 is usually the fastest and is called

The rate of the reaction gradually as the

1.9 mol dm 3 min 1

Time of reaction (min)

0.6 mol dm 3 min 1

Methods of Measuring Reaction Rates

1.1 Measurement of large volume changes

1.1 Measurement of large volume changes

A typical laboratory set-up for measuring the

Volume of gas formed (cm3)

Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)

Time of reaction (min)

H2(g) is sparingly soluble in water while

1.2 Measurement of small volume changes

Liquid phase reaction

1.3 Measurement of mass changes

The cotton wool plug is to allow the escape of CO2(g) but

Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)

CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)

Loss of mass (m)

mfinal = total mass loss

H2O2(aq) + 2H+(aq) + 2I(aq) I2(aq) + 2H2O(l)

colour intensity as reaction proceeds

colour intensity as reaction proceeds

Pairs of opposite colours are complementary

Pairs of opposite colours are complementary

When mixed in the proper proportion,

I0 = intensity before absorption